Modification of fatty oils



V Patented Uct. 13, 1942 MODIFICATION OF FATTY OILS Laszlo Auer, EastOrange, N. J.

No Drawing. Continuation of application Serial No. 318,650, February 12,1940. This application January 22, 1942, Serial No. 427,816

22 Claims.

GENERAL FIELD OF INVENTION The invention relates to modification oforganic isocolloids, and to the modified products.

By isocolloids I mean organic colloidal substances containing mixturesof unsaturated carbon compounds. The dispersed phase and the dispersionmedium of these colloidal systems are both of the same chemicalcomposition but in a different physical state. Organic isocolloids aremixtures of chemically similar organic compounds wherein one or more ofthose compounds, serving as dispersed phase, are dispersed or dissolvedin the others which serve as the dispersion medium of this isocolloidsystem. With such isocolloidal systems (or organic isocolloids) it ispossible, by modification, to change th relative concentration of thedispersed phase and the dispersion medium. For instance, it is possibleto increase the dispersed phase concentration, in which event the amountof the dispersion medium will be correspondingly reduced.

The colloidal transformation brought about in accordance with theinvention apparently involves an alteration in the number, size orphysical state of the colloid aggregations (micelles).

Briefly summarized, the processes according to my invention contemplatedispersion of a modifying agent in the organic isocolloid, and usuallyalso the application of heat. In this Way modification is brought aboutand various characteristics and properties of the starting materials arealtered, the nature and degree of alteration depending upon thetreatment and also upon the nature of the isocolloid used as startingmaterial.

Some of the more important effects of the colloidal transformationsincident to modification are, for example, in the case of fatty oils,changes in drying characteristics, body, viscosity, melting point,elasticity, film strength, etc.

Other changes may also be brought about by treatment in accordance withmy processes.

There are many types of organic isocolloids capable of treatment inaccordance with the broad aspect of the invention, for instance, fattyoils, fatty acids and materials containing the same, i. e., glyceridesof fatty acids whether or not such glycerides also contain other acids;also resins, waxes, tars, pitches, etc.

The present invention is particularly concerned with modification ofglycerides of fatty acids, such as fatty oils, examples of which aregiven hereinafter.

In accordance with the broad aspect of the invention, many differentmaterials and classes thereof may be employed as modifying agents. Ingeneral, these materials are electrolytes or polar compounds. Thepresent application is directed to the use of organic acids as modifyingagents for glycerides of fatty acids, such as fatty oils.

Various features of my improved processes are disclosed and claimed. incopending applications, some of which are mentioned hereinafter. Thesubject matter claimed in the present application is also disclosed inmy prior applications Serial No. 397,279, filed June 9, 1941, and SerialNo. 318,650, filed February 12, 1940. These two applicaticns arecontinuations of earlier applications including Serial Nos. 188,014(Patent 2,244,666), 359,425 (Patent 2,213,944), and 143,- 786 (Patent2,189,772). 3

THE STARTING MATERIAL The fatty oils and similar materials With whichthe present application is especially concerned find one of their mostimportant uses in the varnish industry, where oils having good body anddrying power are very important. The improved products produced inaccordance with this invention also have many other uses.

A list of typical oils which may be advantageously modified by myinvention is as follows:

Tung oil Rapeseed oil Castor oil Walnut oil Linseed oil Pine seed oilFish oil (train oils) Corn oil Poppyseed oil Olive oil Sunflower oil Theease of transformation or modification, under equal conditions,decreases in the order given. That is, the first mentioned oils are mostrapidly modified by my methods, While the oils at the end of the seriesare modified more slowly. However, it should be also mentioned that bythe employment of suitable modifying agents in my methods, even the lastmentioned oils (those at the end of this series) can be profoundlymodified, as Well as those oils appearing in the first of the series.

The foregoing listed, and other fatty oils may The fish oils aremixtures of non-drying and drying triglycerides.

In accordance with the invention, the oils referred to may be treatedper se, or they may be treated in mixtures containing more than one suchoil, or containing other materials. For instance, synthetic resinscontaining natural resins or acids of fatty oils and of resins, may bemodified in accordance with the invention.

In addition, separated fractions of fatty oils (for instance, the betterdrying fractions) may be used as starting materials, either alone ormixed with other oils.

THE MODIFYING AGENT As hereinbefore mentioned, the present applicationis particularly concerned with the use of organic acids as modifyingagents or polar compounds. Such acids may be grouped in various ways, itbeing mentioned that both aliphatic and aromatic organic acids areuseful in my processes, especially those which are lower molecularacids.

In accordance with th foregoing classification, examples are as follows:

Aromatic Aliphatic Formic Acetic. Oxalic Monochloracetic TrichloraceticMalonic Lactic Propionic Butyric Crotonic alic Maleic Succinic TartaricIsovaleric Citric Capric Hydroxyacetic Salicylic Sulpho salicylicPhthalic Benzoic 2:3 hydroxy naphthoic For most purposes, I prefer toemploy relatively low molecular acids, having not more than elevencarbon atoms.

Carboxylic acids are of especial utility, particularly polycarboxylic.One of the best groups is dicarboxylic acids. The carboxylic acids maybe grouped as follows:

Although the acids themselves may be used, where the anhydride iscommercially available, I prefer to use that form of the polycarboxylicacids. For example, phthalic, maleic and succinic anhydrides areavailable.

The polycarboxylic acids, especially dicarboxylic acids having not morethan eight carbon atoms, are particularly suitable for improving thedrying qualities of oils, especially fatty oils of the three classescommonly referred to as nondrying, semi-drying and drying. Examples ofthese three classes of oils are--castor oil, soya bean oil and linseedoil, respectively.

Organic acids are especially advantageous in modifying fatty oils. Forone thing, the modified fatty oil products obtained with the aid of suchacids, dry faster. That is, they have an increased drying velocity ascompared with the original oil. This is advantageous in modifyingnon-drying and semi-drying fatty oils, as Well as in treating dryingoils. Further, in addition to increasing the drying velocity, organicacids also increase the rate of bodying of fatty oils in most cases.That is, fatty oils bodied in the presence of organic acids have agreater body than that of the same oil bodied, alone, under the sameconditions.

TREATMENT CONDITIONS The first step of the process is to mix themodifying agent with the organic isocolloid to be modified, and toproduce an intimate admixture of the two materials. Solid organic acidmodifying agents may be added the form of a dry powder. In such cases,itis advantageous to mill the dry modifying agent with the startingmaterial (organic isocolloid) using any of the known mills, etc., forproducing a colloidal dispersion. If the organic isocolloid is a liquid,such as an oil, the mills used for grinding inks, paints and the like,may be employed. In this way, the solid polar compound may be groundinto and dispersed in the oils, etc. to be modified, Other methods ofdispersing or dissolving the polar compounds in the organic isocolloidsmay also be used. For instance, both the polar compound and the organicisocolloid may be dissolved in a suitable solvent. Again, liquid polarcompounds may be directly mixed with the oils by stirring.

The organic isocolloid and the polar compound may be mixed cold; thatis, at room temperature, when the polar compound is directly soluble inthe organic isocolloid. In such cases, at least some modification may beobtained.

Again, the polar compound and the organic isocolloid may be simplymelted together or fused into a homogeneous mass, if both are readilyfusible .and miscibl with each other. Here too, a modified product isdirectly obtained.

When employing organic acids, the mixture of the isocolloid startingmaterial and the polar compound is preferably heated, the treatmenttemperature being maintained for a shorter or longer period of time,depending upon the nature of modification desired.

Although many modifying agents are capable of use throughout a widepercentage range (for instance from a fractional percentage up to about30%), the organic acids should ordinarily be used in amounts not overabout 10%, for instance, from about .01% to about 5% (based on thestarting material), th preferred range being from .01% to .9%.

As to the temperatures employed, they may be varied over a wide range,although the best results are obtained at temperatures considerablyabove room temperature but below the boiling point of the isocolloid.When using organic acids the temperature should be above about 200 C.,and preferably from about 250 C. to 310 or 320 C.

The time of treatment may also be varied, depending upon the startingmaterial, the treating agent and the result desired. In general,increasing the time of treatment results in more extensive modification.The treatment temperature should ordinarily be maintained for at leastthirty minutes, and preferably for several hours.

The heating of the oil in the presence of the polar compound orelectrolyte (modifying agent) may be done in open vessels and atatmospheric pressure. However, advantageous results are obtained whenthe heating is carried out in closed vessels, such as kettles,autoclaves, pipe coils, etc., to secure the desired modification withthe aid of the polar compound. In such cases, the heating may be carriedout under reduced or increased pressure with advantage. depending uponthe results desired. For instance, heating the mixture under reducedpressure or vacuum, advantageously influences the modification in somecircumstances. Likewise, heating under positive (superatmospheric)pressure also is advantageous (and influences the modification) as whenvolatile solvents or volatile or unstable polar compounds or both areused and the mixture heated above the normal boiling point of suchmaterials. Heating under pressure is also advantageous with certainoils, such as tung oil and the like. For one thing, the pressure assistsin preventing the coagulation or gelling of tung oil which ordinarilyoccurs when tung oil is heated to 260-280 C.

SUPPLEMENTAL TREATMENT CONDITIONS AND AGENTS.

My processes may be practiced in the absence of any additional material,other than the electrolyte or polar compound. However, I have found itis advantageous in some cases to incorporate the electrolyte in thepresence of additional materials which facilitate its incorporation andthe modification of the organic isocolloid. For instance, theelectrolyte may be incorporated in the presence of various organicbodies such as the purely organic additions mentioned post or organicsolvents. Again metal soaps may also be added; for instance siccatives(driers) such as the resinates and linoleates of metal compounds andmetal oxides, commonly used in the varnish industry, as is mentioned inSerial No. 143,786. Further, sulphur or sulphur compounds, such assulphur chloride, etc., may also be used in these processes and added inaddition to the polar compound during the reaction or as an aftertreatment. The sulphur or sulphur compounds effect further modificationand produce sulphurized products. The temperature usually employed formodification (above 200 C.) being substantially above normalvulcanization temperatures, the effect of the sulphur treatment atmodifying temperatures is quite different from vulcanization.

However, I may also efiect vulcanization of my modified products in anafter treatment, so as to produce solid, coherent and elastic products,similar in some characteristics to ordinary rubber. Sulphur may be usedfor this purpose and may be added as such, or in the form of a sulphurcompound, such as sulphur chloride, etc. The action of the sulphur isanalogous to that which takes place in the vulcanization of rubber.Thus, accelerators or activators (zinc oxide, etc.) or both, such asusually employed in the vulcanization of rubber, may be used in myprocesses to accelerate vulcanization when sulphur, etc. is added. Theadded sulphur vulcanizes or sulphurizes my modified products furtherchanging their properties.

When making solid vulcanized rubber-like products, I employ temperaturesbetween 120 and 180 C. for vulcanization, and from to 50 parts ofsulphur to 100 parts of the isocolloid under treatment. Thisvulcanization should be effected after modification, and acceleratorsand antioxidants may be added to the mix in known manner. I may produceliquid vulcanized products as well as rubber-like solids, by regulatingthe amount of sulphur and the time and tempera- 75 ture of heating. Theliquid products are useful as varnish or paint bases.

Two step methods for making vulcanized, modified, heat-bodied fatty oilproducts are described and claimed in my application Serial No. 236,800(Patent 2,234,545). As there stated, many of those products are usefulas rubber substitutes. Others are useful for other purposes, forinstance, in the manufacture of varnishes, lacquers and other liquidcoating compositions, as well as in plastic compositions.

As noted above, the processes may be carried out in various ways, forinstance, either in open or closed vessels as desired. In the lattercase, the air can be entirely or partially displaced by another gas,such as hydrogen, 002, S02, H2S, nitrogen, etc., which influence theresults obtained, these gases being used in supplement to the primarymodifying agent employed. Again, in both cases such gases may be passedthrough the material being treated. That is, the modification can becarried out during the passage of a gas. The gas pressure can be that ofatmospheric. In many cases, however, a vacuum may be used withadvantage. Again, even a higher pressure of several atmospheres is to berecommended in certain cases, it being sometimes advantageous.

That is, I have further found that the results of the process vary withthe nature of the gas present and also with the physical condition(pressure) of this gas. Thus I have found that a certain given startingmaterial which is initially liquid will become slightly viscous only asa result of the electrolyte treatment, if the latter is effected underatmospheric pressure (open vessel) but more viscous if the gas israrefied by the employment of a partial vacuum. In other cases theconverse applies. When plus pressure was used the results differ again.Air gives a different result from another gas or mixtures of gases suchas mentioned ante. The electrolyte treatment may be carried out eitherin the total or partial absence of air, by replacing the same withanother gas, such as those shown ante.

A pressure treatment followed by a vacuum treatment may be used, and Ihave found it to be advantageous to use alternately, atmospheric or pluspressure and vacuum treatment. Such alternate treatment increases theuniformity of the distribution of the electrolyte in the organicisocolloid. In my processes, the gas may be blown or passed through theliquid mass or simply passed over the surface of the same during theheating. It is advisable in some cases, both when open or closed vesselsare employed to have a constant passage of the gas, such as those givenante, during the treatment with electrolyte.

It may be stated with reference to the action of gases, that generallyspeaking rarefication of the gases present, by reduction of pressure inthe vessel in which the treatment is given, tends to intensify theaction of the gases in my processes.

If desired, the electrolyte may be produced in situ, that is, within theorganic isocolloid under treatment, by interaction within the organicisocolloid, of substances capable of reacting under the conditions ofthe process to produce the electrolyte. The same applies to the gas inthe presence of which the organic isocolloid is to be treated and asubstance or substances may be added which evolve the desired gas duringthe processing. It has been found in certain cases that electrolytes andgases which are produced in situ,

being in the nascent state, are somewhat more active than those added inthe pre-formed state.

Likewise, the organic isocolloid itself may be formed in situ during thetreatment. That is, if it is desired to modify an organic isocolloidwhich is not a naturally occurring material and which has to be producedbefore it can be treated, the production of such artificial ormanufactured organic isocolloid may be advantageously combined with thetreatment with the electrolyte. For in- 1 stance, in making modifiedheat-bodied fatty oils, the oil may be both heat-bodied and modified ina single step by heat-bodying the fatty oil in the presence of theelectrolyte or polar compound. To do this several hours heating atpolymerization temperatures is required. Many of my electrolytes areadvantageous for this purpose as they accelerate the heat-bodying andpolymerization of fatty oils.

In addition to the action of electrolytes and the cooperating action ofgases in effecting the colloidal transformations characteristic of myinvention, an additional modification of the ulti mate physicalproperties of the treated products can be effected by the addition tothe material under treatment, of purely (i. e. metal-free) organicbodies, such as phenols, naphthols, naphthalene, chloroform, acetone,alcohols and their homologues and derivatives. These additions aresupplemental to the use of electrolytes. Some of them are solvents andassist in dispersing the electrolyte in the organic isocolloid. The useof solvents for this purpose is also shown in my Serial No. 273,159(Patent 1,985,230) and other prior applications.

I have also found that in my processes the colloidal transformations maybe promoted by the use of rays of oscillating energy, such asultraviolet rays, infra-red rays, X-rays, etc. That is, it isadvantageous to irradiate the oil or other organic isocolloid, before orduring the treatment with electrolyte. Sometimes a subsequent treatmentwith these rays is also helpful. Further, these rays influence andintensify the action of the gases in my processes.

EXAMPLES Example 1 To 100 parts of linseed oil are added parts ofsalicylic acid and the mixture heated in a vac- 1;.

modifying castor oil with this acid, I prefer to employ a lowertemperature, say 270 C., and heat for a longer time.

Likewise, in lieu of the salicylic acid, I may employ other organicacids, such as oxalic, tartaric, citric, etc., disclosed ante, in thepractice of Example 1.

Example 2 In this example, a castor oil having an acid number of 9, isused as the starting material.

1000 parts of this castor oil are heated with 30 parts of salicylic acidat 270 C., for 5 hours in an open kettle.

The modified oil product so obtained is a heavily bodied oil having anacid number of 11. It can be further treated to reduce its acid numberand to increase its body, if desired. In doing so, the oil is furtherheated at 200 C., While bubbling nitrogen through the oil, for twohours. The oil product so obtained has an acid number of 7 and is auseful paint and varnish base.

Example 3 SERIES OF COMPARATIVE TESTS To secure comparative results witha number of difierent organic acids, a series of experiments wasconducted each .under equivalent conditions. These experiments includednot only bodying of the oil in the presence of the organic acid, butalso preparation of a varnish with the bodied oil.

The bodying of the oil and the preparation of the varnish are describedhereinafter under separate headin s.

' BODYING or OIL In all experiments, alkali refined linseed oil wasused, each batch consisting of 1 gallons of oil placed in an aluminum 3gallon (labora tory size) varnish kettle, along with the particular acidmodifying agent.

In each case the treatment was terminated as near as practicable at thattime when th viscosity had reached a certain pre-selected value (V onthe Gardner-Holt varnish scale), thereby giving a comparison of timerequired to body with the different treating agents.

The manner of heating and treating each batch was as follows:

(a) The temperature was raised to about 200 C. in about 30 minutes.

(12) The temperature was held for one hour at 200 C.

(c) The temperature was raised to 300 C.

(d) The temperature was retained at 300 C. for the period of timeindicated in Table No. 1 below.

(6) CO2 gas was bubbled through the batch during steps a, c and d.

The holding at 200 C. (Step b) was employed to ensure giving opportunityfor reaction between the oil and the acid at a temperature below theirboiling or sublimation points.

In the case of each acid used, two experiments were conducted, one with/2% of the acid and the other with 5%, as is indicated in the followingtable:

TABLE No. 1

%% acid 5% acid Time Vis. Time Vis.

Hr. Mm. Hr. Min.

1 3 20 X Benzoic acid 3 20 Z-l 2 2 50 X Citric acid anhydrous 2 45 W 3Citric .H2O.. 3 15 W Citric .HzO 2 30 'I 4 Maleic anhydridc 2 50 UMaloic anhydride 2 W 5 Oxalic acid anhydrous 3 V Oxalic acid anhydro 3 X6 Oxalic .2H O 3 10 V Oxalie .2H 0 2 40 W 7 Salicylic acid 3 Y Salicylicacid 2 Y 8 Tartaric acid anhydrous. 2 30 X Tartaric acid anhydrous 3 V 9Blank alkali refined linseed oil. 3 V Blank alkali refined linseed oil 345 V It will be noted that certain of the acids were tried both in theanhydrous form and also in the form containing water of crystallization.In each such case the anhydrous form manifests somewhat improved resultsover the other form. In addition, it may be noted with reference to No.9 in the above table (blank alkali refined linseed oil) that thisrepresents an experiment conducted under the same conditions, and withthe same oil, but without employment of any modifying agent.

Analysis of the foregoing shows that in the series employing /2% of themodifying agent, the ease of bodying varies from a maximum withanhydrous tartaric acid, to a minimum with the blank, as follows:

Tartaric acid anhydrous Citric acid anhydrous Maleic anhydride Salicylicacid Benzoic acid Citric acid, .H2O

Oxalic acid .2H2O

Oxalic anhydrous Blank alkali refined linseed oil Similarly, with the 5%series, the ease of bodying is as follows:

Maleic anhydride Salicylic acid Citric acid anhydrous Oxalic acid 2H2OCitric acid H20 Oxalic acid anhydrous Benzoic acid Tartaric acidanhydrous Blank alkali refined linseed oil The 5% concentration ofmodifying agent, in most cases, produces faster bodying than does the/z%, the only exceptions being anhydrous citric acid and anhydroustartaric acid, which apparently body faster with /2 In connection withthe above grading of the oils in accordance with ease of bodying, it isnoted that the deviations in viscosity from the pre-selected value (V)were ignored and that some of the examples would have occupied differentpositions in th grading lists had their bodying been terminated exactlyat the pre-selected viscosity (V) The foregoing results indicatesubstantial improvement in bodying as a result of the employment of amodifying agent. In this connection it should be kept in mind thatcustomarily an effort would be made to body varnish oils to a viscosityas high as from Z4 to Z6 (Gardner scale), which is considerably abovethe approximate V viscosity pre-selected for testing in the aboveexperiments. In the higher viscosities even better results would bedemonstrated. The V viscosity was pre-selected for the present purposes,since preparation of varnishes with oil of this viscosity facilitatesmeasurement of differences in the varnish cooking, the cookingexperiments being referred to hereinafter.

Further characteristics of the bodied oils are indicated in Table No. 2just below:

TABLE No. 2

ACID SAPONIFI- IODINE NUMBER CATION VAL. NUMBER Acid l Benzoic acid 3.34.4 194 194 129 122 2 Citric acid anhydrous 3. 8 6. 0 197 199 134 134 3Citric acid .HQO..- 4.1 5.4 195.4 198.4 129 138.5 4 Maleic acidanhydride 4.1 10 196 206 138 5 Oxalic acid anhydrous 4.4 5.4 193 196132.5 135.5 6 Oxalic acid .2H;O 3.0 3.6 204.5 194.5 137 130.3 7Salicylic acid 4.1 4.1 197 143 131 8 Tartaric acid anhydrous 3.6 5.0 200199 135 131 9 Blank alkali refined linseed 011.. 3.05 191. 7 132PREPARATION or VARNISH The bodied oil of each experiment referred to inthe foregoing series was cooked to a varnish, with each of threedifferent resins:

I. Ester gum (glycerine ester of rosin).

II. Rosin modified maleic alkyl resin (Amberol 801).

III. Rosin modified phenol-formaldehyde resin (Paranol 1750).

In each case the varnish was of 25 gallon oil .length (in the proportionof 25 gallons of oil to 100 pounds of the resin), each batch beingprepared to yield /2 gallon for laboratory tests. Each batch was thinnedwith mineral spirits to 50% solids and the cooking time was adjusted soas to yield a viscosity of C to H on the Gardner scale (brushingconsistency).

Observations on the bodying of the varnishes with the three differentresins are as follows:

I. Ester gum series In most cases the oils treated with 5% of the acidindicated bodying of the varnishes with ester gum faster than where theoils were treated with 12% of the acid. In this series the varnishesbodied in about three-quarters of the time required for equivalentbodying of a varnish containing the blank control alkali refined linseedoil (bodied without modifying agent). The follow-,

ing show-ed particularly good results, the list being graded from thetop:

Per cent Maleic anhydride (best) 5 Benzoic acid 5 Salicylic acidSalicylic acid 5 Oxalic acid, containing crystal water 5 II. Rosinmodified maleic alkyd resin series Per cent Maleic anhydride (best) 5OXalic acid, with crystal water 5 Anhydrous citric acid Salicylic acidBenzoic acid 5 Salicylic acid 5 Anhydrous citric acid 5 III. Rosinmodified phenol-formaldehyde resin series In this series the varnishescontaining acid treated oils bodied in about two-thirds the timerequired for the varnish containing the blank control alkali refinedlinseed oil. The best eX- amples are graded as follows:

Per cent Maleic anhydride (best) 5 Salicylic acid /2 Salicylic acid 5Maleic anhydride /2 Benzoic acid 5 Benzoic acid /2 Oxalic acid, withcrystal water /2 OXalic acid, with crystal water 5 All of the foregoingvarnishes were also tested for other characteristics, and in most casesdisplayed improvement in other respects, when compared with thevarnishes prepared with the blank control alkali refined linseed oil. Tosecure comparative results, the same driers were used with each Varnish.This drier was as follows:

1. Lead 0.3% 2. Cobalt 0.03% 3. Manganese 0.02%

all as naphthenate solutions, the percentage of metal specifiedindicating metal content based on the content of oil in the varnish.

The prepared varnishes were then tested for:

(a) Drying (5) Cold water resistance Boiling Water resistance ((1)Alkali resistance For test purposes the varnish film was applied to asteel plate by means of a spreading knife, providing a film thickness of0.0015".

Observations of the foregoing tests were as follows (a) DRYING In mostinstances the varnishes containing acid treated 011s displayednoticeably improved drying characteristics when compared with varnishcontaining the blank control alkali refined linseed oil. Whenconsidering the varnishes made with all three of the resins abovementioned, the oil treated with anhydrous tartaric acid indicated thebest general improvement. Almost equivalent results were shown in thecase of the varnishes containing 5% maleic anhydride and 5% salicylicacid.

A second series of comparative varnish tests was conducted withincreased drier content both in the blank control varnish as well as inthe others (0.8% lead, 0.08% cobalt and 0.04% manganese), but thisseries displayed results very similar to the above and are, therefore,not separately analyzed herein.

(1)) COLD WATER RESISTANCE (c) BOILING WATER RESISTANCE These tests wereconducted in accordance with A. S. T. M. standard methods, andreasonably good characteristics were displayed by all of the varnishes.

(d) ALKALI RESISTANCE This test was carried out by immersing test plates(carrying films dried for 48 hours) in a 3% aqueous sodium hydroxidesolution. As in the drying tests, the varnish containing tartaric acidmanifested the best general improvement with all three resins.Particularly good results were also indicated with /g% anhydrous citricacid and oxalic acid, containing crystal water, when used with the estergum and the maleic resin.

In connection with the bodying of oils in the comparative seriesdiscussed above, it may be mentioned that no glycerine was added tocompensate for acidity. Ordinarily, where an appreciable quantity ofacid is present, for instance 5%, glycerine should be added to the oilsin order to neutralize the excess acidity and lower the acid value. Inthe foregoing examples, alkali resistance would have been improved bythis expedient.

The following additional general observations may be made with referenceto the foregoing comparative tests:

1. With respect to drying time, the best results are indicated withanhydrous tartaric acid, 5% maleic anhydride, and 5% salicylic acid.

2. In general, increase in concentration of the acid modifying agentslightly improves drying time, although in a few cases drying was betterwith the lower concentration.

3. With respect to bodying time, best results are secured with tartaricacid, maleic anhydride, citric acid and salicylic acid.

4. The aromatic acids, such as benzoic and salicylic, are more readilysoluble in the oils than are the aliphatic acids. This is a distinctadvantage. Although some aromatic acids display a tendency towardsublimation, this tendency is at a minimum with the higher molecularacids such as the carboxylic acids, especially of the naphthaleneseries, and also of anthracene, anthraquinone, phenanthrene orphenanthraquinone and/or their derivatives.

5. The aliphatic acids have less tendency toward sublimation than do thearomatic acids. (Where appreciable sublimation tends to occur,precautions should be taken to avoid loss of reagent, as by effectingthe treatment in a manner to return Sublimated agent to the reactionmass.)

Examples 4-10 In another series of comparative experiments certainuniform treatment conditions were adopted, as follows:

In each case, the oil employed was linseed oil and 5% of the treatingagent was used.

In each case, the heating time was in the neighborhood of 5 hours. Inconducting these experiments the approximate reaction temperature was300 C., although there were minor differences between various of theexperiments. The treatment temperature was between about 290 to 310 C.

A control experiment was also conducted under the same heatingconditions, but without treating agent, so as to secure comparativeresults.

The experiments in this group may be divided into pairs, the twoexperiments of each pair employing the same treating agent. Thedifference between the treatment of the two members of each pair was asfollows:

1. Heating a 300 gram charge in a one liter distilling flask undervacuum-identified herebelow by the letter (a) following the examplenumber.

2. Heating a or 300 gram charge in a 500 c. 0. open enameledbeaker-identified he'rebelow by the letter (1)) following the examplenumber.

Example 4(a) Citric acid containing water of crystallization The mixturefrothed and bumped slightly during rise in temperature, but then boiledsteadily and gradually darkened in color, finally yielding ayellow-brown oil which, on cooling, was a thickish liquid of consistencysimilar to that of thin treacle.

Example 4(b) Citric acid containing water of crystallization Somefrothing and gas evolution, and slight bumping occurred, during rise intemperature, but the liquid steadied itself at the treatment temperature(approximately 300 C.). The cooled product was a thick elastic jelly,brown in color with a strong green fluorescence. In the residue, alittle of the reagent remained as a charred mass.

Example 5 (a) Oxalc'c acid Gas evolution become very rapid during risein temperature, especially at about 180 C., but the batch steadied withgradual solution of the treating agent. The product was a thinnish oilwith a light brown color. A small portion (about 0.75 gram) of the agentremained like sand in the flask.

Example 5 (b) Oxalic acid The product was similar in color to Example5(a) but slightly thinner.

Example 6 (a) Phthalic anhydridc Some sublimation occurred during risein temperature and the heating was suspended and then restarted, afterwhich the liquid boiled steadily. The product was a pale yellow materialsimilar in appearance and consistency to Vaseline.

Example 6(b) Phthalic anltydride Example '7 (b) Salicylic acid Somesublimation occurred at about 230 0., but on reaching reactiontemperature slight boiling and gradual thickening took place. Theproduct was a thick viscous liquid of dark brown color.

Example 8(a) Benaoic acid During rise in temperature sublimationoccurred and vigorous bumping continued for several hours at treatmenttemperature. After some irregular boiling the liquid steadied. Theproduct was a medium thin brown oil, with a green fluorescence.

Example 8 (b) Benzoic acid Sublimation occurred during rise intemperature and on reaching treatment temperature the oil boiled gentlyand gradually thickened. The product was a thick viscous product similarto that of Example 7(a) Example 9 (a) M onochloracetic acid During risein temperature gas was evolved and some distillation occurred. Uponreaching treatment temperature the mixture boiled steadily, withoutdistillation, and the color darkened. Shortly after reaching treatmenttemperature distillation again set in and continued for about one hour,but gradually tapered 'off. The product was a thick brown oil with astrong green fluorescence. The distillate was a black oil with anobnoxious smell.

Example 9(b) M onochloracetic acid The product was a mobile browncolored oil, with a stron dull green fluorescence.

Example 10(a) Amino salicylic acid At low temperature, in theneighborhood of 70 0., very bad frothing and some distillation occurred,but the batch gradually subsided as treatment temperature was approachedand the mixture then boiled vigorously. The product was a fairly thickgolden brown oil with a strong green fluorescence.

Example 10(1)) Amino salicylic acid Considerable frothing occurred asthe temperature rose, although the frothing gradually subsided and wassteady at the reaction temperature. The product was a thick dark brownoil with a strong dark green fluorescence.

With reference to Examples 4 to 10 inclusive, it is mentioned that theviscosity of all of the products was higher than the product of theblank control experiment. The consistency in most of the cases wasrecorded and comparison thereof indicates the -following graduation inviscosity, the product of highest viscosity appearing at'the top of thelist:

Example Benzoic acid. Citric acid with water of crystallization.

Amino salicylic acid.

Salicylic acid. Amino salicylic acid.

Monochloracetic acid. Beta-oxynaphthoic acid. Oxalic acid. Phthalicanhydride. Salicylic acid. Monochloracctic acid.

Citric acid with water of crystallization.

Benzoic acid.

Oxalic acid.

Blank control.

Soft solid Thick viscous Medium viscous (liquid) Thin liquid As tocolor, it is mentionedthat the following were as light as the color ofthe blank control experiment Example 4 (a) Citric acid with water ofcrystallization. 8(a) Benzoic acid. (1)) Oxalic acid.

Example Citric acid with water of crystallization. Salicylic acid.

Phthalic anhydride.

Benzoic acid.

Amino salicylic acid.

Example 11 5% of beta-oxynaphthoic acid was added to 300 grams oflinseed oil and the mixture heated under vacuum for about 5 hours atfrom 290 to 300 C. The mixture frothed considerably at the start andupon reaching about 130 C. a fairly violent reaction took place, thisreaction subsiding at about 150 C. and giving way to a rapid gasevolution and apparent gradual solution of the reagent. Upon furtherincrease in temperature, to about 270 C., some distillation took place,but this stopped by the time the boiling temperature was reached, andupon attaining the reaction temperature the batch remained steadythroughout the five hour treatment period.

The product was a light brown oil with a strong green fluorescence.

Example 12 1000 parts of the same castor oil as used in Example 2(having an acid number of 9) were heated with 2 parts of sulphosalicylicacid and parts of glycerine, in an autoclave, to 270 C. while slowlybubbling CO2 through the mixture and maintaining a vacuum of 50 mm. Hgon the autoclave. under vacuum for one hour. Then the temperature wasreduced to 250 C. and the mixture maintained at that temperature for twohours. Finally the temperature was dropped to 200 C. and the mixtureheld at this temperature until the modification was completed, about twohours at 200 C. being required. During all of these beatings, theintroduction of the CO2 gas was so controlled as not to destroy thedesired vacuum.

The modified castor oil so obtained has good drying properties and anacid number of 3.2. It is useful in making paints and varnishes.

In the above specification the increased drying velocity of oils, e. g.if treated according to the disclosed processes with modifying agents,means always a comparison with an oil, treated in the absence of suchpolar compounds, but otherwise under similar conditions. The oils, whenheated to polymerizing temperatures, change their body, viscosity and tolesser degree also their drying The mixture was so heated at 270 C. r

velocity. The action of the polar compounds may I be observed if wecompare the resulting product to an oil, treated under similarconditions, heated to the same temperature and for the same time, but inthe absence of polar compounds. The increased rate of drying frequentlycauses also an increased rate of bodying of the oils, all otherconditions being equal.

During my processes complex changes usually occur, in the presence ofacidic polar compounds as a result of which new, improved modifiedproducts are obtained from fatty oils, resins and the other isocolloidsas described ante as useful starting materials in my processes. Forinstance, if oils, resins and other compounds containing high molecularacids or derivatives of such acids are heated to temperatures above 200C. water and hydrogen may be given off by the starting material,accompanied by complicated changes in those starting materials, such ascondensation, polymerization, shifting of double bonds, dehydroxylation,decarboxylation, amongst others. In any event in my processes suchchanges as result in increasing the drying velocity and effecting otherimprovements in the properties of the starting materials are acceleratedby the presence and action of my aforesaid polar compounds; at leastbeneficial and desirable results are obtained, although it is impossibleto ascertain the exact mechanism by which they are obtained in eachparticular commercial embodiment of my present invention.

I claim:

1. In the manufacture of improved, modified products, suitable forplastic and coating compositions, from fatty oils, fatty acids, estersof fatty acids, and from material containing the same, said modifiedproducts having increased drying velocity and other improved properties,the step which comprises heating said materials in the presence of aminor amount of an organic acid at a temperature of at least 200 C. andfor a time sufficient to modify the physical properties of and increasethe drying velocity of said materials, said heating being continued forat least thirty minutes and the amount of said organic acid being notmore than 5%.

2. The process of claim 1, wherein the organic acid is an aromatic acid.

3. The process of claim 1, wherein the organic acid is an aliphaticacid.

4. The process of claim 1, wherein said material is a fatty oil andwherein the organic acid is a carboxylic acid.

5. The process of claim 1, wherein said material is a fatty oil andwherein the organic acid is a polycarboxylic acid.

6. The process of claim 1, wherein said material is a fatty oil andwherein the organic acid is a dicarboxylic acid.

'7. The process of claim 1, wherein the organic acid is salicylic acid.

8. The process of claim 1, wherein the organic acid is benzoic acid.

9. The process of claim 1, wherein the organic acid is chosen from theclass consisting of maleic acid and its anhydride.

10. The process of claim 1, wherein said material is a fatty oil.

11. The process of claim 1, where said material is a non-drying oil.

12. The process of claim 1, wherein said material is a semi-drying oil.

13. The process of claim 1, wherein said material is a drying oil.

14. The process of claim 1, wherein said material is castor oil.

15. The process of claim 1, wherein said material is soya bean oil.

16. The process of claim rial is linseed oil.

1'7. The process of claim 1, wherein said material is castor oil andsaid organic acid is chosen from the class consisting of maleic acid andits anhydride.

18. The process of claim 1, wherein said material is soya bean oil andsaid organic acid is chosen from the class consisting of maleic acid andits anhydride.

19. The process of claim 1, wherein said material is linseed oil andsaid organic acid is chosen from the class consisting of maleic acid andits anhydride.

20. The process of claim 1, wherein said organic acid is used in anamount from .01% to .9%.

1, wherein said mate- 21. The process of claim 1, wherein said materialis a fatty oil and wherein said material is also treated with analcohol.

22. In the manufacture of improved, modified products, suitable forplastic and coating compositions, from fatty oils, fatty acids, estersof iatty acids, and from materials containing the same, said modifiedproducts having increased drying velocity and other improved properties,the step which comprises heating said materials in the presence of aminor amount of an organic acid at a temperature of at least 200 C. andfor a time sufficient to modify the physical properties of and increasethe drying velocity of said materials, said heating being continued forat least thirty minutes and the amount of said organic acid being notmore than 10%.

LAszL AUER.

a CERTIFICATE OF co ERECTION. Patent No. 2,298,911 I I October 1 191 2.

msz o AUER.

d that error appears in the printed specification tion as follows: Page5, secfor "alkyl" read --alkyd-; page 7 second column,

a --Examp1e 7(b)--; and that the said Let ti on therein that the samemay ,It' is hereby certifie of the above mimbered patent requiringcorrec 0nd column, line 25, line 10, for "Example '((a)'' tea 11ersPatent should be read with 'this 'correc cord of the case in the PatentOffice.

conform to the-re 214th day of November, A. D. 19 42.

Signed and s ealedthis Henry Van Arsdale,

*(Seal) Acting Commissioner of Patents. hi i iv 0#',

